This study presents a comprehensive evaluation of the tribological behavior of cylinder liners and piston rings—key components in internal combustion engines (ICEs). Experiments were conducted using a pin-on-disc wear tester under varying loads (50–100 N) and speeds (175–350 rpm) to determine the coefficient of friction (μ) and wear rate. The selected pin and disc materials represent real engine components to ensure realistic operating conditions. Before and after each experiment, the cylinder liner-piston ring pair was cleaned with acetone to ensure accurate measurement of mass loss. Surface roughness (Ra, Rq, Rz, µm) was assessed using a Mahr M-1 profilometer, and Brinell hardness tests were carried out using a digital optical Brinell hardness testing machine to determine the mechanical properties of the contact surfaces. The results revealed that safflower oil achieved the lowest coefficient of friction at higher speeds, with an 18% reduction compared with conventional 20W-50 engine oil. Camelina oil, camelina biodiesel and safflower biodiesel each exhibited a reduction of approximately 12.5% in friction, highlighting their potential as viable alternatives to petroleum-based lubricants.